Arthur zitscher



Patented Mar. 5, 1929..

ARTHUR ZI'ISCHEB, OF OFFENBACH-ON-THE-MAIN, GERMANY, ASSIGIIOB T G313!!-SELLI DYESTUFF CORPORATION, OF NEW YORK, -l\T. Y., A CORI ORATION 0FDELAWARE.

PROCESS FOR IEANUFACTURING ORIHO-AMINODIARYLETHERS.

1\To Drawing. Application filed December 16, 1927, Serial No. 240,631,and in Germany December 24, 1926.

wherein R means an arylresidue of the henzene naphthalene or anthraceneseries and the benzene nucleus may contain further substituents, areobtained by my process in agood yield and in a very, pure state. Theyare valuable intermediates for the production of dyestuffs.

The course oi reaction is surprising in View of the well knowninactivity of the aromatic hydroxycon'ipounds, particularly of thenegatively substituted ones. My process produces, when using nuclearsubstituted components besides ortho-aminodiphenylether itself itssubstitution products partly unknown hitherto. I

In order to further illustrate my invention the following examples aregiven, the parts being by weight and all temperatures in centigradedegrees. But I wish to be understood that I am not limited to theparticular conditions nor to the specific products mentioned therein.

Example 1.

water-bath. In this manner the ortho-nitrodlphenylether of the formula:

is obtained as a clear yellow oil, which may be purified bydistillation. It boils at 195-197 at 45 mm. pressure as described inliterature (cf. American Chem. Soc, vol. 38, page 1534).

Nhen reduced in the usual manner it yields the ortho-aminodiphenyletherof the for- \NH2 which may be purified by distillation. WVhenrecrystallized from ligroine, it melts at 41 (ct. Chem. Soc., Vol. 127,page 54d).

is obtained with a good yield. crystallized from corrected).

When carrying out the condensation with addition ofspirit by shortlyheating the mass under reflux, the yield is almost a theoretical one.

249,5 parts of the formed 5-chloro-2-nitro diphenyletherare introducedin a boiling reducing mixture, consisting of 250 parts of cast-ironborings, 50 parts of glacial acetic acid and 1000 parts of water, andthe mass is When respirit it melts at 85 (not boiled, until the reactionis finished. The

chloro-2-aminodiphenylether of the formula:

thus formed is isolated in the usual manner. hen recrystallized fromligroin it melts at l0- l l (not corr cted), as described in theaforesaid literature (of. Chem. Soc, vol. 127, page 5452).

Example 3.

A. solution of l? parts of 2.e-dichlorophenolate of soda in spirit ismixed with an alcoholic solution of 81. parts ofF3.4-.-dinitr-:)-'lchlorobenzene and the mixture is heated for some timeon the water-bath. In this manner the5.2.5-trichloro-Q-nitrodiphenylether of the formula:

is obtained, melting at 97-98", when recrystallized from spirit. Onreduction it yields the 5.2.5-trichloro-2--am1nodipl'ienylether of theformula:

B oi melting at 74-75 (not corrected), when recrystallized from dilutespirit. Both compounds are new products.

In the same manner f. i. 5-chloro-2-nitr0- phenyl-B-naphthylother of theformula:

melting at 1Ot-l10 (not corrected) when re crystallized from diluteacetone, and 5-chlo- 1 0-2-aminophenyl-fl-naphthylether of the formulaCl Q 7 NH2 melting at- 108109, when recrystallized from ligroine, areobtained. As further new prod ucts, obtainable according to my processmay be named: 5.4-dichloro-Q-nitrodiphenylether of the formula:

melting point 81 (not corrected) from ligroine, and5.41-diehloro-2-aminodiphenyL ether of the formula:

in which formulaR means an arylresidue and the benzene nucleus maycontain further substituents, which process comprises actingwith analkali metal salt' of an hydroxycompound of the aromatic series onortho-dinitrocompounds of the benzene series and treating theortho-nitrodiarylethers thus formed with reducing agents.

2. Process for manufacturing ortho-aminodiarylethers of the generalformula:

in which formula R means an arylresidue and the benzene nucleus maycontain further substituents, which process comprises acting with analkali metal salt of an hydroxycompound of the aromatic'series inpresence of a diluent on ortho-dinitrocompounds of the benzene seriesand treating the ortlio-nitrodiarylethers thus formed with reducingagents.

Process for manufacturing ortho-aniinodiarylethers of the generalformula:

Nru

in which formula R means an arylresidue, wiich process comprisesactingWith an alkali metal salt of an hydroxycompound 0f the aromatic serieson 3.4-dinitro-l-chloroF benzene and treating theortho-nitrodiarylothers thus formed with reducing agents.

i. In the process for producing orthoaminodiarylethers the manufactureof orthonitrodiarylethers of the general formula:

Cit

in which formula R means an aryli'esidue and the benzene nucleus maycontain further substituents, Which comprises acting W1th an alkalimetal salt of an hydroxycompound of the aromatic series onortho-dinitrocompounds of the benzene series.

5. Process for manufacturing ortho-aminocliarylethers of the generalformula:

in which i'ioi'mulaat least the benzene nucleus signified by H ischlon'natecl, which process comprisesactingwith an alkali metal salt ofa chlorinated hydroxycompouncl of the aromatic series onortho-chnitrocompouncls of the benzene series and treating theorthonitrocliarylethers thus formed with reducing agents.

6. Process for manufacturing- 5.2.5-trichloro-2-aminodiphenylether ofthe formula:

ARTHUR ZITS CHER.

